WO2022160493A1 - Recovery method and use of crude ferro-nickel alloy - Google Patents
Recovery method and use of crude ferro-nickel alloy Download PDFInfo
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- WO2022160493A1 WO2022160493A1 PCT/CN2021/091665 CN2021091665W WO2022160493A1 WO 2022160493 A1 WO2022160493 A1 WO 2022160493A1 CN 2021091665 W CN2021091665 W CN 2021091665W WO 2022160493 A1 WO2022160493 A1 WO 2022160493A1
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- Prior art keywords
- nickel
- iron
- ammonia
- recovery method
- leaching
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000011084 recovery Methods 0.000 title claims abstract description 41
- 229910000863 Ferronickel Inorganic materials 0.000 title abstract description 5
- 229910045601 alloy Inorganic materials 0.000 title abstract 4
- 239000000956 alloy Substances 0.000 title abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 127
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 122
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 65
- 229910052742 iron Inorganic materials 0.000 claims abstract description 57
- 238000002386 leaching Methods 0.000 claims abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000012141 concentrate Substances 0.000 claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001710 laterite Inorganic materials 0.000 claims description 12
- 239000011504 laterite Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- -1 ferrous metals Chemical class 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 abstract description 16
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 abstract description 16
- 229940053662 nickel sulfate Drugs 0.000 abstract description 8
- 238000000498 ball milling Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- 239000007853 buffer solution Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910017709 Ni Co Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XEEYBQQBJWHFJM-RNFDNDRNSA-N iron-60 Chemical compound [60Fe] XEEYBQQBJWHFJM-RNFDNDRNSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000037390 scarring Effects 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention belongs to the field of non-ferrous metallurgy, and particularly relates to a recovery method and application of a crude nickel-iron alloy.
- Nickel is an important strategic metal, which is widely used in key materials and high-tech fields such as stainless steel, superalloy, fuel cells, etc.
- the source of nickel resources is mainly nickel sulfide ore and nickel oxide ore (ie laterite nickel ore) in crustal resources. ) two kinds, of which 30% are nickel sulfide ore and 70% are laterite nickel ore.
- the production of nickel is in short supply, and the high-quality nickel sulfide ore is gradually being mined, which makes the mining and application of laterite nickel ore become more and more extensive.
- Laterite nickel ore has become the main raw material for the production of ferronickel products.
- the process principles of processing different ores can be summarized as: (1) fire process; (2) wet ammonia leaching process; (3) wet pressure acid leaching process.
- the fire process requires a higher nickel grade, and for laterite nickel ore with a nickel content of about 1%, the wet ammonia leaching process can be used.
- the problems of higher requirements, high consumption of auxiliary materials, serious scarring of the pressurizing valve, and high operating and production costs directly restrict the development of the enterprise.
- the wet ammonia leaching process has weak corrosive materials, weak equipment material requirements, easy processing and production, and adopts atmospheric pressure leaching, the equipment structure is simple, and the reagents can be recycled.
- the laterite nickel ore is pyrometallurgized to obtain crude nickel-iron alloy, and then the crude nickel-iron alloy is used to prepare other nickel-iron products.
- the ammonia leaching process is the key process, and the ammonia leaching process and leaching effect are directly Determine the recovery rate of metal elements such as nickel and iron.
- the nickel metal recovery rate is generally about 80%. If nickel-iron alloy powder is used with conventional ammonium carbonate and ammonium bicarbonate systems, the leaching rate is generally about 90%. And the purity of the iron concentrate obtained is less than 80%.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. Therefore, the present invention proposes a method and application for the recovery of crude nickel-iron alloy, which can realize the recovery of crude nickel-iron alloy (nickel 15%-40%, iron 60%-85%, sulfur 1-1.5%, carbon 1.4% -2%, silicon 0.5-0.8%) nickel is converted into nickel sulfate, iron is converted into iron powder, and the comprehensive reuse of resources is realized, and the recovery rate of iron is more than 99.99%, and the recovery rate of nickel is more than 94%.
- the present invention adopts the following technical solutions:
- a method for recovering crude nickel-iron alloy comprising the following steps:
- step (1) adding an alkaline buffer to the nickel complex leaching solution to adjust the pH to an alkaline reaction, heating and steaming ammonia to obtain nickel sulfate; in step (1), the ammonium salt is ammonium sulfate or ammonium hydrogen sulfate at least one of them.
- the crude nickel-iron alloy is obtained by reducing and roasting laterite nickel ore, and the content of nickel in the crude nickel-iron alloy is 15%-40%, and the content of iron is 60%-85%. %, the content of sulfur is 1-1.5%, the content of carbon is 1.4-2%, and the content of silicon is 0.5-0.8%.
- the ball is milled to a particle size of less than 100 mesh.
- the temperature is raised to 40° C. ⁇ 200° C.
- the pressure of pressurization is 0.5 MPa ⁇ 1.5 MPa
- the reaction time is 2 h ⁇ 10 h.
- the atmosphere of the ammonia immersion is circulating air, and the flow rate of the air is controlled to be 1.0-3.0 L/min. This provides the oxygen required for the reaction.
- step (1) the ammonium salt and ammonia water are mixed to obtain a leaching solution, and the liquid-solid ratio of the leaching solution and the crude nickel-iron alloy is (3-6): 1 mL/g.
- the stirring speed is 150r/min ⁇ 400r/min.
- the pH of the slurry is 9.5-11.
- the total ammonia concentration is 4mol/L ⁇ 9mol/L
- the ammonium salt is ammonium sulfate
- the molar ratio of the ammonium ion to the sulfate radical is (2-5):1.
- the reducing agent is a carbon source; the carbon source is at least one of carbon powder, starch or glucose.
- the mass ratio of the iron slag to the reducing agent is 100:(1-10).
- the roasting temperature is 200°C-600°C, and the roasting time is 2-8h.
- the purity of the iron concentrate is greater than 98%, and the nickel content is less than 0.05%.
- the alkaline buffer is at least one of sodium hydroxide, potassium hydroxide or sodium carbonate.
- the concentration of the alkaline buffer is 1-5 mol/L
- the pH adjustment to alkaline is to adjust the pH to 9-10.
- the temperature of the reaction is 60°C to 90°C, and the reaction time is 3 to 7 hours.
- step (3) the ammonia water obtained after the ammonia distillation is cooled is reused for ammonia leaching.
- the method further includes performing evaporative crystallization to obtain nickel sulfate hexahydrate.
- the present invention also provides the application of the above-mentioned recovery method in recovering non-ferrous metals.
- Crude nickel-iron alloy of the present invention is through crushing and grinding-pressurized ammonia leaching-filtering-evaporative crystallization, adopts sulfuric acid system in the pressurized ammonia leaching, and can directly obtain high-value class I nickel sulfate hexahydrate after ammonia leaching and steaming ammonia ( Purity of 99.7%), and high-grade saleable refined iron powder (recovery rate greater than 99.99%, purity greater than 98%), the ammonia-containing vapor generated during the ammonia leaching process can be reused after condensation, and nickel sulfate products are generated by evaporative crystallization , No waste water and slag, the nickel-iron alloy is made into a high-value product.
- the present invention has short technological process, easy-to-control technical conditions, and simple operation, and the nickel in the nickel-iron alloy is made into the product nickel sulfate hexahydrate in one process.
- FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
- Crude nickel-iron alloy from a laterite nickel ore processing plant in Indonesia (the composition of the crude nickel-iron alloy is: Fe 64%, Ni 33%, C 1.2%, S 1.7%) 100g is crushed, and then Use a ball mill to grind the nickel-iron alloy particle size to less than 100 mesh (>95%);
- Ammonia water and ammonium sulfate system are configured into leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid ratio of leachate and nickel-iron alloy is 3:1mL/g, and total ammonia concentration is 6mol/L, wherein sulfate radical and ammonia
- the measured iron ore contains 0.34% nickel and 92.3% iron, which can be directly sold as a product;
- the leaching rate of nickel in the above-mentioned nickel complex leaching solution can reach 95.8%, and the leaching rate of iron is less than 0.2%.
- a small amount of 2mol/L sodium hydroxide solution is added to adjust the pH to 9.5.
- 80 °C Ammonia distillation was carried out to finally obtain a nickel sulfate solution with a nickel concentration of 55 g/L, which was then passed through a rotary evaporator to obtain nickel sulfate hexahydrate.
- Table 1 shows the content of each element in the iron concentrate of Example 1. From Table 1, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 92.3%, which can be directly sold as a product.
- Table 2 is the content of each element in the nickel sulfate hexahydrate of Example 1, available from Table 2, the recovery rate of nickel in the crude nickel-iron alloy is 94.71%, and the nickel content is 21.17%, and the nickel sulfate hexahydrate of Example 2 can be used for the preparation of ternary precursors.
- Fig. 1 is the process flow diagram of embodiment 1, as can be obtained from the figure, through crushing and grinding-pressurized ammonia leaching-filtration-evaporation crystallization, obtain high-value nickel sulfate product, and high-grade fine iron powder that can be sold.
- Ammonia water and ammonium sulfate system are configured as leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid ratio of leachate and nickel-iron alloy is 4:1mL/g, and total ammonia concentration is 5mol/L, wherein sulfate radical and ammonia
- the measured iron ore contains 0.34% nickel and 92.3% iron, which can be directly sold as a product;
- the leaching rate of nickel in the nickel complex leaching solution can reach 95.8%, and the leaching rate of iron is less than 0.2%.
- a small amount of 2mol/L sodium hydroxide solution is added to adjust the pH to 9.5, and the leaching rate is carried out at 80 °C.
- Ammonia was distilled to finally obtain a nickel sulfate solution with a nickel concentration of 55 g/L, and then through a rotary evaporator, nickel sulfate hexahydrate was obtained.
- Table 3 shows the content of each element in the iron concentrate of Example 2. From Table 3, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 93.1%, which can be directly sold as a product.
- Table 4 is the content of each element in the nickel sulfate hexahydrate of Example 2, available from Table 4, the recovery rate of nickel in the crude nickel-iron alloy is 95.71%, and the nickel content is 21.09%, and the nickel sulfate hexahydrate of Example 2 can be used for the preparation of ternary precursors.
- Ammonia water and ammonium sulfate system are configured into leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid ratio of leachate and nickel-iron alloy is 5:1mL/g, and total ammonia concentration is 7mol/L, wherein sulfate radical and ammonia
- the leaching rate of nickel in the nickel complex leaching solution can reach 95.8%, and the leaching rate of iron is less than 0.2%.
- a small amount of 2mol/L sodium hydroxide solution is added to adjust the pH to 9.5, and the leaching rate is carried out at 80 °C.
- Ammonia was distilled to finally obtain a nickel sulfate solution with a nickel concentration of 55 g/L, and then through a rotary evaporator, nickel sulfate hexahydrate was obtained.
- Table 5 shows the content of each element in the iron concentrate of Example 3. From Table 5, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 93.1%, which can be directly sold as a product.
- Table 6 is the content of each element in the nickel sulfate hexahydrate of Example 3, available from Table 6, the recovery rate of nickel in the crude nickel-iron alloy is 94.91%, the nickel content is 21.11%, and the nickel sulfate hexahydrate can be used for the ternary precursor body preparation.
- a method for recovering a crude nickel-iron alloy of this comparative example comprises the following steps:
- iron slag is washed with water, 5g of carbon powder is added, and calcined at 500 ° C for 3 hours to obtain iron concentrate.
- the iron ore measured contains 0.34% nickel and 90.3% iron, which can be directly sold as a product;
- the leaching rate of nickel in the nickel complex leaching solution is 83.75%, and the leaching rate of iron is less than 0.2%, to obtain a nickel complex solution with a nickel concentration of 25g/L, and then add a small amount of 2mol/L sodium hydroxide solution Adjust the pH to 9.5, filter, wash and dry to obtain the product nickel oxide.
- Table 5 shows the content of each element in the iron concentrate of Comparative Example 1. From Table 5, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 90.3%, which can be directly sold as a product.
- Table 8 is the content of each element in the nickel oxide of Comparative Example 1, available from Table 8, the recovery rate of nickel in the crude nickel-iron alloy is 89.91%, and the nickel content is 76.3%, but the nickel oxide is highly toxic and needs to be sold. It can be used for the preparation of ternary precursors after acid-soluble conversion into solution ratio.
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Abstract
The present invention belongs to the field of nonferrous metallurgy. Disclosed are a recovery method and the use of a crude ferro-nickel alloy. The recovery method comprises the following steps: crushing and ball-milling crude ferro-nickel alloy, adding ammonium salt and ammonia water, and mixing and stirring same, heating and pressurizing for an ammonia leaching reaction to obtain a slurry, and filtering same to obtain a nickel complex leaching solution and iron slag; adding a reducing agent into the iron slag, and carrying out reduction roasting to obtain iron ore concentrate; and adding an alkaline buffer solution into the nickel complex leaching solution to adjust the pH value for an alkaline reaction, and heating for ammonia distillation to obtain nickel sulfate. The crude ferro-nickel alloy of the present invention is subjected to crushing and ore grinding, pressurized ammonia leaching, filtering and evaporative crystallization, a sulfuric acid system is used in pressurized ammonia leaching, and after ammonia leaching and ammonia distillation, high-value class I nickel sulfate hexahydrate (the purity being 99.7%) and high-grade marketable refined iron powder (the recovery rate being greater than 99.99%, and the purity being greater than 98%) can be directly obtained.
Description
本发明属于有色冶金领域，具体涉及一种粗制镍铁合金的回收方法和应用。The invention belongs to the field of non-ferrous metallurgy, and particularly relates to a recovery method and application of a crude nickel-iron alloy.
镍是一种重要的战略金属，广泛应用于不锈钢、高温合金、燃料电池等关键材料和高新技术领域，目前镍资源的来源主要是地壳资源中的硫化镍矿和氧化镍矿(即红土镍矿)两种，其中30％为硫化镍矿、70％为红土镍矿。且随着不锈钢产业的快速发展，使镍的生产供不应求，优质硫化镍矿逐渐开采殆尽，促使红土镍矿的开采应用变得越发广泛。Nickel is an important strategic metal, which is widely used in key materials and high-tech fields such as stainless steel, superalloy, fuel cells, etc. At present, the source of nickel resources is mainly nickel sulfide ore and nickel oxide ore (ie laterite nickel ore) in crustal resources. ) two kinds, of which 30% are nickel sulfide ore and 70% are laterite nickel ore. And with the rapid development of the stainless steel industry, the production of nickel is in short supply, and the high-quality nickel sulfide ore is gradually being mined, which makes the mining and application of laterite nickel ore become more and more extensive.
进入21世纪以来，新能源行业的兴起，不锈钢产业的饱和，促使作为不锈钢行业主要的添加剂镍铁急需运用于新能源行业，目前全球有色金属中，镍的消耗量仅次于铜、铝、铅、锌，居有色金属第五位。Since the beginning of the 21st century, the rise of the new energy industry and the saturation of the stainless steel industry have prompted an urgent need for nickel-iron as the main additive in the stainless steel industry to be used in the new energy industry. At present, among the global non-ferrous metals, the consumption of nickel is second only to copper, aluminum and lead. , Zinc, ranking fifth in non-ferrous metals.
红土镍矿已经成为生产镍铁产品的主要原料。处理不同矿石的工艺原则流程可归纳为：(1)火法流程；(2)湿法氨浸流程；(3)湿法加压酸浸流程。火法流程要求较高的镍品位，而对于镍含量在1％左右的红土镍矿则可采用湿法氨浸流程，如用湿法加压酸浸流程，生产工艺复杂、工艺环节、对设备的要求较高、辅料消耗高、加压阀结疤严重、运营生产成本高等问题，直接制约着企业的发展。而选择湿法氨浸流程物料腐蚀性弱，设备材质要求较弱，易于加工制作，并采用常压浸出，设备结构简单，试剂可循环使用。Laterite nickel ore has become the main raw material for the production of ferronickel products. The process principles of processing different ores can be summarized as: (1) fire process; (2) wet ammonia leaching process; (3) wet pressure acid leaching process. The fire process requires a higher nickel grade, and for laterite nickel ore with a nickel content of about 1%, the wet ammonia leaching process can be used. The problems of higher requirements, high consumption of auxiliary materials, serious scarring of the pressurizing valve, and high operating and production costs directly restrict the development of the enterprise. However, the wet ammonia leaching process has weak corrosive materials, weak equipment material requirements, easy processing and production, and adopts atmospheric pressure leaching, the equipment structure is simple, and the reagents can be recycled.
在红土镍矿冶炼过程中，首先将红土镍矿火法冶金，得到粗制镍铁合金，再利用粗制镍铁合金制备成其他镍铁产品，氨浸工艺是关键工序，氨浸过程、浸出效果直接决定镍、铁等金属元素回收率的高低。而目前的氨浸出过程中，若直接用红土矿作为原料镍金属回收率一般在80％左右，若用镍铁合金粉配以常规的碳酸铵、碳酸氢铵体系，浸出率一般在90％左右，且得到铁精矿纯度不到80％。In the smelting process of laterite nickel ore, firstly, the laterite nickel ore is pyrometallurgized to obtain crude nickel-iron alloy, and then the crude nickel-iron alloy is used to prepare other nickel-iron products. The ammonia leaching process is the key process, and the ammonia leaching process and leaching effect are directly Determine the recovery rate of metal elements such as nickel and iron. In the current ammonia leaching process, if laterite ore is used directly as the raw material, the nickel metal recovery rate is generally about 80%. If nickel-iron alloy powder is used with conventional ammonium carbonate and ammonium bicarbonate systems, the leaching rate is generally about 90%. And the purity of the iron concentrate obtained is less than 80%.
发明内容SUMMARY OF THE INVENTION
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种粗制镍铁合金的回收方法和应用，该方法能够实现将粗制镍铁合金(镍15％-40％，铁 60％-85％，硫1-1.5％，碳1.4-2％，硅0.5-0.8％)中的镍转化为硫酸镍，铁转化为铁粉，实现资源的综合回用，且铁的回收率为99.99％以上，镍的回收率为94％以上。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. Therefore, the present invention proposes a method and application for the recovery of crude nickel-iron alloy, which can realize the recovery of crude nickel-iron alloy (nickel 15%-40%, iron 60%-85%, sulfur 1-1.5%, carbon 1.4% -2%, silicon 0.5-0.8%) nickel is converted into nickel sulfate, iron is converted into iron powder, and the comprehensive reuse of resources is realized, and the recovery rate of iron is more than 99.99%, and the recovery rate of nickel is more than 94%.
为实现上述目的，本发明采用以下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种粗制镍铁合金的回收方法，包括以下步骤：A method for recovering crude nickel-iron alloy, comprising the following steps:
(1)将粗制镍铁合金破碎、球磨，再加入铵盐和氨水混合搅拌，升温加压进行氨浸反应，得到浆料，过滤，即得镍络合物浸出液和铁渣；(1) Crude nickel-iron alloy is crushed, ball-milled, and then ammonium salt and ammonia water are added to mix and stir, and the temperature rises and pressurizes to carry out ammonia leaching reaction to obtain slurry, and filter to obtain nickel complex leaching solution and iron slag;
(2)在所述铁渣中加入还原剂，进行还原焙烧，得到铁精矿；(2) adding reducing agent in described iron slag, carry out reduction roasting, obtain iron concentrate;
(3)在所述镍络合物浸出液中加入碱性缓冲液调pH至碱性反应，加热蒸氨，即得硫酸镍；步骤(1)中，所述铵盐为硫酸铵或硫酸氢铵中的至少一种。(3) adding an alkaline buffer to the nickel complex leaching solution to adjust the pH to an alkaline reaction, heating and steaming ammonia to obtain nickel sulfate; in step (1), the ammonium salt is ammonium sulfate or ammonium hydrogen sulfate at least one of them.
优选地，步骤(1)中，所述粗制镍铁合金是将红土镍矿经还原焙烧所得，所述粗制镍铁合金中镍的含量为15％-40％，铁的含量为60％-85％，硫的含量为1-1.5％，碳的含量为1.4-2％，硅的含量为0.5-0.8％。Preferably, in step (1), the crude nickel-iron alloy is obtained by reducing and roasting laterite nickel ore, and the content of nickel in the crude nickel-iron alloy is 15%-40%, and the content of iron is 60%-85%. %, the content of sulfur is 1-1.5%, the content of carbon is 1.4-2%, and the content of silicon is 0.5-0.8%.
优选地，步骤(1)中，所述球磨至粒径小于100目。Preferably, in step (1), the ball is milled to a particle size of less than 100 mesh.
优选地，步骤(1)中，所述升温至40℃～200℃，加压的压力0.5MPa～1.5MPa，反应的时间为2h～10h。Preferably, in step (1), the temperature is raised to 40° C.˜200° C., the pressure of pressurization is 0.5 MPa˜1.5 MPa, and the reaction time is 2 h˜10 h.
优选地，步骤(1)中，所述氨浸的氛围为循环通入空气，所述通入空气的流量控制为1.0-3.0L/min。以此提供反应所需要的氧气。Preferably, in step (1), the atmosphere of the ammonia immersion is circulating air, and the flow rate of the air is controlled to be 1.0-3.0 L/min. This provides the oxygen required for the reaction.
优选地，步骤(1)中，所述铵盐和氨水混合得到浸出液，所述浸出液和粗制镍铁合金的液固比为(3-6)：1mL/g。Preferably, in step (1), the ammonium salt and ammonia water are mixed to obtain a leaching solution, and the liquid-solid ratio of the leaching solution and the crude nickel-iron alloy is (3-6): 1 mL/g.
优选地，步骤(1)中，所述搅拌的速度为150r/min～400r/min。Preferably, in step (1), the stirring speed is 150r/min～400r/min.
优选地，步骤(1)中，所述浆料的pH为9.5～11。Preferably, in step (1), the pH of the slurry is 9.5-11.
优选地，步骤(1)中，所述氨浸反应的过程中，总氨浓度为4mol/L～9mol/L，当所述铵盐为硫酸铵时，所述铵离子与硫酸根的摩尔比为(2-5)：1。Preferably, in step (1), in the process of the ammonia leaching reaction, the total ammonia concentration is 4mol/L～9mol/L, and when the ammonium salt is ammonium sulfate, the molar ratio of the ammonium ion to the sulfate radical is (2-5):1.
优选地，步骤(2)中，所述还原剂为碳源；所述碳源为碳粉、淀粉或葡萄糖中的至少一种。Preferably, in step (2), the reducing agent is a carbon source; the carbon source is at least one of carbon powder, starch or glucose.
优选地，步骤(2)中，所述铁渣和还原剂的质量比为100：(1-10)。Preferably, in step (2), the mass ratio of the iron slag to the reducing agent is 100:(1-10).
优选地，步骤(2)中，所述焙烧的温度为200℃-600℃，焙烧时间为2-8h。Preferably, in step (2), the roasting temperature is 200°C-600°C, and the roasting time is 2-8h.
优选地，步骤(2)中，所述精铁矿纯度大于98％，其中镍含量小于0.05％。Preferably, in step (2), the purity of the iron concentrate is greater than 98%, and the nickel content is less than 0.05%.
优选地，步骤(3)中，所述碱性缓冲液为氢氧化钠、氢氧化钾或碳酸钠中的至少一种。Preferably, in step (3), the alkaline buffer is at least one of sodium hydroxide, potassium hydroxide or sodium carbonate.
优选地，步骤(3)中，所述碱性缓冲液的浓度为1～5mol/L，所述调pH至碱性是将pH调至9～10。Preferably, in step (3), the concentration of the alkaline buffer is 1-5 mol/L, and the pH adjustment to alkaline is to adjust the pH to 9-10.
优选地，步骤(3)中，所述反应的温度为60℃～90℃，反应的时间为3～7h。Preferably, in step (3), the temperature of the reaction is 60°C to 90°C, and the reaction time is 3 to 7 hours.
优选地，步骤(3)中，所述蒸氨冷却后得到的氨水重新用于氨浸。Preferably, in step (3), the ammonia water obtained after the ammonia distillation is cooled is reused for ammonia leaching.
优选地，步骤(3)中，所述蒸氨后还包括进行蒸发结晶，得到六水硫酸镍。Preferably, in step (3), after the ammonia distillation, the method further includes performing evaporative crystallization to obtain nickel sulfate hexahydrate.
本发明的反应原理：Reaction principle of the present invention:
2Ni+O
2+8NH
3+2(NH
4)
2SO
4——2[Ni(NH
3)
6]SO
4+2H
2O
2Ni+O 2 +8NH 3 +2(NH 4 ) 2 SO 4 ——2[Ni(NH 3 ) 6 ]SO 4 +2H 2 O
2Co+O
2+8NH
3+2(NH
4)
2SO
4——2[Co(NH
3)
6]SO
4+2H
2O
2Co+O 2 +8NH 3 +2(NH 4 ) 2 SO 4 ——2[Co(NH 3 ) 6 ]SO 4 +2H 2 O
4Fe
2++O
2+2H
2O+8OH
-——4Fe(OH)
3↓。
4Fe 2+ +O 2 +2H 2 O+8OH − —— 4Fe(OH) 3 ↓.
本发明还提供上述的回收方法在回收有色金属中的应用。The present invention also provides the application of the above-mentioned recovery method in recovering non-ferrous metals.
相对于现有技术，本发明的有益效果如下：With respect to the prior art, the beneficial effects of the present invention are as follows:
1.本发明粗制镍铁合金经过破碎磨矿-加压氨浸-过滤-蒸发结晶，加压氨浸中采用硫酸体系，氨浸蒸氨后可直接得到高价值的Ⅰ类六水硫酸镍(纯度为99.7％)，以及高品位可出售的精铁粉(回收率大于99.99％，纯度大于98％)，氨浸过程中产生的含氨蒸汽冷凝后可以重复利用，硫酸镍产品通过蒸发结晶生成，无废水废渣，将镍铁合金制成了高价值的产品。1. Crude nickel-iron alloy of the present invention is through crushing and grinding-pressurized ammonia leaching-filtering-evaporative crystallization, adopts sulfuric acid system in the pressurized ammonia leaching, and can directly obtain high-value class I nickel sulfate hexahydrate after ammonia leaching and steaming ammonia ( Purity of 99.7%), and high-grade saleable refined iron powder (recovery rate greater than 99.99%, purity greater than 98%), the ammonia-containing vapor generated during the ammonia leaching process can be reused after condensation, and nickel sulfate products are generated by evaporative crystallization , No waste water and slag, the nickel-iron alloy is made into a high-value product.
2.本发明工艺流程短，技术条件易控，操作简单，一道工序便将镍铁合金中的镍制成了产品六水硫酸镍。2. The present invention has short technological process, easy-to-control technical conditions, and simple operation, and the nickel in the nickel-iron alloy is made into the product nickel sulfate hexahydrate in one process.
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with the accompanying drawings and embodiments, wherein:
图1为本发明的实施例1的工艺流程图。FIG. 1 is a process flow diagram of Embodiment 1 of the present invention.
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of The scope of protection of the present invention.
实施例1Example 1
本实施例的粗制镍铁合金的回收方法，包括以下步骤：The recovery method of the crude nickel-iron alloy of the present embodiment comprises the following steps:
(1)粗制镍铁合金(取自印尼某红土镍矿加工厂产品)(粗制镍铁合金中的成分为：Fe 64％，Ni 33％，C 1.2％，S 1.7％)100g进行破碎，再采用球磨机球磨至镍铁合金粒径小于100目(＞95％)；(1) Crude nickel-iron alloy (from a laterite nickel ore processing plant in Indonesia) (the composition of the crude nickel-iron alloy is: Fe 64%, Ni 33%, C 1.2%, S 1.7%) 100g is crushed, and then Use a ball mill to grind the nickel-iron alloy particle size to less than 100 mesh (>95%);
(2)将氨水与硫酸铵体系配置成浸出液，加入上述球磨后的镍铁合金中，浸出液和镍铁合金的液固比为3:1mL/g，总氨浓度为6mol/L，其中硫酸根与氨根摩尔浓度比为1:2，加入密闭反应容器中，搅拌转速为400r/min，反应30min后开始通空气并加热，空气的流量为1.5L/min，温度为140℃，进行氨浸反应6h，反应结束后检测浆料pH＝9.8，并趁热过滤，即得镍络合物浸出液和铁渣；(2) Ammonia water and ammonium sulfate system are configured into leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid ratio of leachate and nickel-iron alloy is 3:1mL/g, and total ammonia concentration is 6mol/L, wherein sulfate radical and ammonia The molar concentration ratio is 1:2, put it into a closed reaction vessel, the stirring speed is 400r/min, after 30min of reaction, the air is passed through and heated, the air flow rate is 1.5L/min, the temperature is 140℃, and the ammonia immersion reaction is carried out for 6h. , after the reaction, the slurry pH=9.8 was detected, and filtered while hot to obtain nickel complex leachate and iron slag;
(3)将铁渣经水洗后，再加入5g碳粉，在500℃条件下煅烧3h，得到铁精矿，测的铁矿中含镍0.34％，含铁92.3％，可作为产品直接出售；(3) After washing the iron slag with water, add 5g of carbon powder, and calcined at 500 ° C for 3 hours to obtain iron concentrate. The measured iron ore contains 0.34% nickel and 92.3% iron, which can be directly sold as a product;
(4)上述镍络合物浸出液中镍的浸出率可达95.8％，铁的浸出率小于0.2％，同时补加少量2mol/L的氢氧化钠溶液调pH至9.5，在80℃的条件下进行蒸氨，最终得到镍浓度为55g/L的硫酸镍溶液，再经过旋转蒸发仪，得到六水硫酸镍。(4) The leaching rate of nickel in the above-mentioned nickel complex leaching solution can reach 95.8%, and the leaching rate of iron is less than 0.2%. At the same time, a small amount of 2mol/L sodium hydroxide solution is added to adjust the pH to 9.5. Under the condition of 80 °C Ammonia distillation was carried out to finally obtain a nickel sulfate solution with a nickel concentration of 55 g/L, which was then passed through a rotary evaporator to obtain nickel sulfate hexahydrate.
表1：实施例1的铁精矿中各元素含量Table 1: Content of each element in the iron concentrate of Example 1
| FeFe | NiNi | CoCo | SiSi | CuCu | CrCr | |
| 含量/％content/% | 92.392.3 | 0.340.34 | 0.080.08 | 0.370.37 | 0.040.04 | 0.110.11 |
| 回收率/％Recovery rate/% | 99.9999.99 | 0.710.71 | 0.170.17 | 99.9999.99 | 99.9999.99 | 99.9999.99 |
表1为实施例1的铁精矿中各元素含量，从表1可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为92.3％，可作为产品直接出售。Table 1 shows the content of each element in the iron concentrate of Example 1. From Table 1, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 92.3%, which can be directly sold as a product.
表2：六水硫酸镍产品中各元素含量Table 2: Contents of elements in nickel sulfate hexahydrate products
| NiNi | CoCo | MnMn | FeFe | CuCu | CrCr | |
| 含量/％content/% | 21.1721.17 | 0.090.09 | 0.0010.001 | 0.0020.002 | 0.0010.001 | 0.0010.001 |
| 回收率/％Recovery rate/% | 94.7194.71 | 98.1498.14 | 57.2357.23 | 0.0010.001 | 0.0010.001 | 0.0010.001 |
表2为实施例1的六水硫酸镍中各元素含量，从表2可得，粗制镍铁合金中镍的回收率为94.71％，镍含量为21.17％，实施例2的六水硫酸镍可用于三元前驱体的制备。Table 2 is the content of each element in the nickel sulfate hexahydrate of Example 1, available from Table 2, the recovery rate of nickel in the crude nickel-iron alloy is 94.71%, and the nickel content is 21.17%, and the nickel sulfate hexahydrate of Example 2 can be used for the preparation of ternary precursors.
图1为实施例1的工艺流程图，从图中可得，经过破碎磨矿-加压氨浸-过滤-蒸发结晶，得到高价值的硫酸镍产品，以及高品位可出售的精铁粉。Fig. 1 is the process flow diagram of embodiment 1, as can be obtained from the figure, through crushing and grinding-pressurized ammonia leaching-filtration-evaporation crystallization, obtain high-value nickel sulfate product, and high-grade fine iron powder that can be sold.
实施例2Example 2
本实施例的粗制镍铁合金的回收方法，包括以下步骤：The recovery method of the crude nickel-iron alloy of the present embodiment comprises the following steps:
(1)取粗制镍铁合金(取自印尼某红土镍矿加工厂产品)(镍铁合金中的成分为：Fe 64％，Ni 33％，C 1.2％，S 1.7％)100g进行破碎，再采用球磨机球磨至镍铁合金的粒径小于100目(粒径小于100目的占比＞95％)；(1) Take 100g of crude nickel-iron alloy (from a laterite nickel ore processing plant in Indonesia) (the composition of nickel-iron alloy is: Fe 64%, Ni 33%, C 1.2%, S 1.7%) for crushing, and then use The particle size of the nickel-iron alloy is less than 100 mesh (the proportion of particle size less than 100 mesh is > 95%);
(2)将氨水与硫酸铵体系配置成浸出液，加入上述球磨后的镍铁合金中，浸出液和镍铁合金的液固比为4:1mL/g，总氨浓度为5mol/L，其中硫酸根与氨根摩尔浓度比为1:3，加入密闭反应容器中，搅拌转速为400r/min，反应30min后开始通空气并加热，空气的流量为1.5L/min，温度为140℃，进行氨浸反应6h，反应结束后检测浆料pH＝9.8，并趁热过滤，即得镍络合物浸出液和铁渣；(2) Ammonia water and ammonium sulfate system are configured as leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid ratio of leachate and nickel-iron alloy is 4:1mL/g, and total ammonia concentration is 5mol/L, wherein sulfate radical and ammonia The molar concentration ratio is 1:3, put it into a closed reaction vessel, the stirring speed is 400r/min, after 30min of reaction, the air is passed through and heated, the air flow rate is 1.5L/min, the temperature is 140℃, and the ammonia immersion reaction is carried out for 6h , after the reaction, the slurry pH=9.8 was detected, and filtered while hot to obtain nickel complex leachate and iron slag;
(3)将铁渣经水洗后，再加入5g碳粉，在500℃条件下煅烧3h，得到铁精矿，测的铁矿中含镍0.34％，含铁92.3％，可作为产品直接出售；(3) After washing the iron slag with water, add 5g of carbon powder, and calcined at 500 ° C for 3 hours to obtain iron concentrate. The measured iron ore contains 0.34% nickel and 92.3% iron, which can be directly sold as a product;
(4)镍络合物浸出液中镍的浸出率可达95.8％，铁的浸出率小于0.2％，同时补加少量2mol/L的氢氧化钠溶液调pH至9.5，在80℃的条件下进行蒸氨，最终得到镍浓度为55g/L的硫酸镍溶液，再经过旋转蒸发仪，得到六水硫酸镍。(4) The leaching rate of nickel in the nickel complex leaching solution can reach 95.8%, and the leaching rate of iron is less than 0.2%. At the same time, a small amount of 2mol/L sodium hydroxide solution is added to adjust the pH to 9.5, and the leaching rate is carried out at 80 °C. Ammonia was distilled to finally obtain a nickel sulfate solution with a nickel concentration of 55 g/L, and then through a rotary evaporator, nickel sulfate hexahydrate was obtained.
表3：铁精矿中各元素含量Table 3: Contents of Elements in Iron Concentrates
| FeFe | NiNi | CoCo | SiSi | CuCu | CrCr | |
| 含量/％content/% | 93.193.1 | 0.240.24 | 0.020.02 | 0.580.58 | 0.030.03 | 0.210.21 |
| 回收率/％Recovery rate/% | 99.9999.99 | 0.540.54 | 0.150.15 | 99.9999.99 | 99.9999.99 | 99.9999.99 |
表3为实施例2的铁精矿中各元素含量，从表3可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为93.1％，可作为产品直接出售。Table 3 shows the content of each element in the iron concentrate of Example 2. From Table 3, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 93.1%, which can be directly sold as a product.
表4：六水硫酸镍产品中各元素含量Table 4: Contents of elements in nickel sulfate hexahydrate products
| NiNi | CoCo | MnMn | FeFe | CuCu | CrCr | |
| 含量/％content/% | 21.0921.09 | 0.110.11 | 0.0020.002 | 0.0020.002 | 0.0010.001 | 0.0010.001 |
| 回收率/％Recovery rate/% | 95.7195.71 | 97.1497.14 | 43.7343.73 | 0.0010.001 | 0.0010.001 | 0.0010.001 |
表4为实施例2的六水硫酸镍中各元素含量，从表4可得，粗制镍铁合金中镍的回收率为95.71％，镍含量为21.09％，实施例2的六水硫酸镍可用于三元前驱体的制备。Table 4 is the content of each element in the nickel sulfate hexahydrate of Example 2, available from Table 4, the recovery rate of nickel in the crude nickel-iron alloy is 95.71%, and the nickel content is 21.09%, and the nickel sulfate hexahydrate of Example 2 can be used for the preparation of ternary precursors.
实施例3Example 3
本实施例的粗制镍铁合金的回收方法，包括以下步骤：The recovery method of the crude nickel-iron alloy of the present embodiment comprises the following steps:
(1)取粗制镍铁合金(镍铁合金中的成分为：Fe 64％，Ni 33％，C 1.2％，S 1.7％)100g进行破碎，再采用球磨机球磨至镍铁合金粒径小于100目(粒径小于100目的占比＞95％)；(1) Take 100 g of crude nickel-iron alloy (the composition in the nickel-iron alloy is: Fe 64%, Ni 33%, C 1.2%, S 1.7%) for crushing, and then use a ball mill to grind the nickel-iron alloy to a particle size of less than 100 mesh (grain size). diameter less than 100 mesh (>95%);
(2)将氨水与硫酸铵体系配置成浸出液，加入上述球磨后的镍铁合金中，浸出液和镍铁合金的液固比为5:1mL/g，总氨浓度为7mol/L，其中硫酸根与氨根摩尔浓度比为1:4，其中测得溶液pH＝10.8，加入密闭反应容器中，搅拌转速为500r/min，反应30min后开始通空气并加热，空气的流量为2.5L/min，温度为180℃，进行氨浸反应8h，反应结束后检测浆料pH＝10.8，并趁热过滤，即得镍络合物浸出液和铁渣；(2) Ammonia water and ammonium sulfate system are configured into leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid ratio of leachate and nickel-iron alloy is 5:1mL/g, and total ammonia concentration is 7mol/L, wherein sulfate radical and ammonia The root molar concentration ratio is 1:4, wherein the solution pH=10.8 is measured, added to the closed reaction vessel, the stirring speed is 500r/min, and the air is vented and heated after the reaction for 30min, the flow of the air is 2.5L/min, and the temperature is 180 ℃, carry out ammonia leaching reaction for 8h, after the reaction is over, check the pH of the slurry = 10.8, and filter while hot to obtain nickel complex leaching solution and iron slag;
(3)将铁渣经水洗后，再加入10g葡萄糖，在400℃条件下煅烧6h，得到铁精矿，测的铁矿中含镍0.26％，含铁93.1％，可作为产品直接出售；(3) After washing the iron slag with water, add 10 g of glucose, and calcinate at 400 ° C for 6 hours to obtain iron concentrate. The iron ore measured contains 0.26% nickel and 93.1% iron, which can be directly sold as a product;
(4)镍络合物浸出液中镍的浸出率可达95.8％，铁的浸出率小于0.2％，同时补加 少量2mol/L的氢氧化钠溶液调pH至9.5，在80℃的条件下进行蒸氨，最终得到镍浓度为55g/L的硫酸镍溶液，再经过旋转蒸发仪，得到六水硫酸镍。(4) The leaching rate of nickel in the nickel complex leaching solution can reach 95.8%, and the leaching rate of iron is less than 0.2%. At the same time, a small amount of 2mol/L sodium hydroxide solution is added to adjust the pH to 9.5, and the leaching rate is carried out at 80 °C. Ammonia was distilled to finally obtain a nickel sulfate solution with a nickel concentration of 55 g/L, and then through a rotary evaporator, nickel sulfate hexahydrate was obtained.
表5：铁精矿中各元素含量Table 5: Content of each element in iron concentrate
| FeFe | NiNi | CoCo | SiSi | CuCu | CrCr | |
| 含量/％content/% | 93.193.1 | 0.260.26 | 0.040.04 | 0.740.74 | 0.090.09 | 0.310.31 |
| 回收率/％Recovery rate/% | 99.9999.99 | 0.730.73 | 0.170.17 | 99.9999.99 | 99.9999.99 | 99.9999.99 |
表5为实施例3的铁精矿中各元素含量，从表5可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为93.1％，可作为产品直接出售。Table 5 shows the content of each element in the iron concentrate of Example 3. From Table 5, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 93.1%, which can be directly sold as a product.
表6：六水硫酸镍中各元素含量Table 6: Content of each element in nickel sulfate hexahydrate
| NiNi | CoCo | MnMn | FeFe | CuCu | CrCr | |
| 含量/％content/% | 21.1121.11 | 0.050.05 | 0.0010.001 | 0.0020.002 | 0.0010.001 | 0.0010.001 |
| 回收率/％Recovery rate/% | 94.9194.91 | 94.1494.14 | 62.7762.77 | 0.0010.001 | 0.0010.001 | 0.0010.001 |
表6为实施例3的六水硫酸镍中各元素含量，从表6可得，粗制镍铁合金中镍的回收率为94.91％，镍含量为21.11％，六水硫酸镍可用于三元前驱体的制备。Table 6 is the content of each element in the nickel sulfate hexahydrate of Example 3, available from Table 6, the recovery rate of nickel in the crude nickel-iron alloy is 94.91%, the nickel content is 21.11%, and the nickel sulfate hexahydrate can be used for the ternary precursor body preparation.
对比例1Comparative Example 1
本对比例的一种粗制镍铁合金的回收方法，包括以下步骤：A method for recovering a crude nickel-iron alloy of this comparative example comprises the following steps:
(1)取粗制镍铁合金(镍铁合金中的成分为：Fe 64％，Ni 33％，C 1.2％，S 1.7％)100g进行破碎，再采用球磨机球磨至镍铁合金粒径小于100目(粒径小于100目的占比＞95％)；(1) Take 100 g of crude nickel-iron alloy (the composition in the nickel-iron alloy is: Fe 64%, Ni 33%, C 1.2%, S 1.7%) for crushing, and then use a ball mill to grind the nickel-iron alloy to a particle size of less than 100 mesh (grain size). diameter less than 100 mesh (>95%);
(2)将氨水与碳酸铵体系配置成浸出液，加入上述球磨后的镍铁合金中，浸出液和镍铁合金的液固为3:1mL/g，总氨浓度为6mol/L，其中碳酸根与氨根摩尔浓度比为1:2，加入密闭反应容器中，搅拌转速为400r/min，反应30min后开始通空气并加热，空气的流量为1.5L/min，温度为140℃，进行氨浸反应6h，反应结束后检测浆料pH＝9.8，并趁热过滤，即得镍络合物浸出液和铁渣；(2) ammonia water and ammonium carbonate system are configured into leaching solution, add in the nickel-iron alloy after above-mentioned ball milling, the liquid-solid of leachate and nickel-iron alloy is 3:1mL/g, total ammonia concentration is 6mol/L, wherein carbonate radical and ammonia radical The molar concentration ratio is 1:2, put it into a closed reaction vessel, and the stirring speed is 400r/min. After 30min of reaction, the air is passed through and heated. After the reaction, the slurry pH=9.8 was detected, and filtered while hot to obtain nickel complex leachate and iron slag;
(3)将铁渣经水洗后，再加入5g碳粉，在500℃条件下煅烧3h，得到铁精矿，测 的铁矿中含镍0.34％，含铁90.3％，可作为产品直接出售；(3) After the iron slag is washed with water, 5g of carbon powder is added, and calcined at 500 ° C for 3 hours to obtain iron concentrate. The iron ore measured contains 0.34% nickel and 90.3% iron, which can be directly sold as a product;
(4)镍络合物浸出液中镍的浸出率为83.75％，铁的浸出率小于0.2％，得到镍浓度为25g/L的镍络合溶液，再补加少量2mol/L的氢氧化钠溶液调pH至9.5，过滤、洗涤、烘干后得到产品氧化镍。(4) The leaching rate of nickel in the nickel complex leaching solution is 83.75%, and the leaching rate of iron is less than 0.2%, to obtain a nickel complex solution with a nickel concentration of 25g/L, and then add a small amount of 2mol/L sodium hydroxide solution Adjust the pH to 9.5, filter, wash and dry to obtain the product nickel oxide.
表7：铁精矿中各元素含量Table 7: Content of each element in iron concentrate
| FeFe | NiNi | CoCo | SiSi | CuCu | CrCr | |
| 含量/％content/% | 90.390.3 | 1.741.74 | 0.140.14 | 0.540.54 | 0.130.13 | 0.410.41 |
| 回收率/％Recovery rate/% | 99.9999.99 | 1.331.33 | 0.240.24 | 99.9999.99 | 99.9999.99 | 99.9999.99 |
表5为对比例1的铁精矿中各元素含量，从表5可得，粗制镍铁合金中铁的回收率为99.99％，铁含量为90.3％，可作为产品直接出售。Table 5 shows the content of each element in the iron concentrate of Comparative Example 1. From Table 5, the recovery rate of iron in the crude nickel-iron alloy is 99.99%, and the iron content is 90.3%, which can be directly sold as a product.
表8：氧化镍中各元素含量Table 8: Contents of Elements in Nickel Oxide
| NiNi | CoCo | MnMn | FeFe | CuCu | CrCr | |
| 含量/％content/% | 76.376.3 | 1.51.5 | 0.030.03 | 0.020.02 | 0.020.02 | 0.010.01 |
| 回收率/％Recovery rate/% | 89.9189.91 | 87.1487.14 | 52.7752.77 | 0.0010.001 | 0.0010.001 | 0.0010.001 |
表8为对比例1的氧化镍中各元素含量，从表8可得，粗制镍铁合金中镍的回收率为89.91％，镍含量为76.3％，但是氧化镍有剧毒，需要出售资质，需要经过酸溶转化为溶液配比后才能用于三元前驱体的制备。Table 8 is the content of each element in the nickel oxide of Comparative Example 1, available from Table 8, the recovery rate of nickel in the crude nickel-iron alloy is 89.91%, and the nickel content is 76.3%, but the nickel oxide is highly toxic and needs to be sold. It can be used for the preparation of ternary precursors after acid-soluble conversion into solution ratio.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge possessed by those of ordinary skill in the art, various Variety. Furthermore, the embodiments of the present invention and features in the embodiments may be combined with each other without conflict.
Claims (10)
- 一种粗制镍铁合金的回收方法，其特征在于，包括以下步骤：A method for recovering crude nickel-iron alloy, comprising the following steps:(1)将粗制镍铁合金破碎、球磨，再加入铵盐和氨水混合搅拌，升温加压进行氨浸反应，得到浆料，过滤，即得镍络合物浸出液和铁渣；(1) Crude nickel-iron alloy is crushed, ball-milled, and then ammonium salt and ammonia water are added to mix and stir, and the temperature rises and pressurizes to carry out ammonia leaching reaction to obtain slurry, and filter to obtain nickel complex leaching solution and iron slag;(2)在所述铁渣中加入还原剂，进行还原焙烧，得到铁精矿；(2) adding reducing agent in described iron slag, carry out reduction roasting, obtain iron concentrate;(3)在所述镍络合物浸出液中加入碱性缓冲液调pH至碱性反应，加热蒸氨，即得硫酸镍；步骤(1)中，所述铵盐为硫酸铵或硫酸氢铵中的至少一种。(3) adding an alkaline buffer to the nickel complex leaching solution to adjust the pH to an alkaline reaction, heating and steaming ammonia to obtain nickel sulfate; in step (1), the ammonium salt is ammonium sulfate or ammonium hydrogen sulfate at least one of them.
- 根据权利要求1所述的回收方法，其特征在于，步骤(1)中，所述粗制镍铁合金是将红土镍矿经还原焙烧所得，所述粗制镍铁合金中镍的含量为15％～40％，铁的含量为60％～85％，硫的含量为1-1.5％，碳的含量为1.4-2％，硅的含量为0.5-0.8％。The recovery method according to claim 1, characterized in that, in step (1), the crude nickel-iron alloy is obtained by reducing and roasting laterite nickel ore, and the content of nickel in the crude nickel-iron alloy is 15% to 15%. 40%, the content of iron is 60%-85%, the content of sulfur is 1-1.5%, the content of carbon is 1.4-2%, and the content of silicon is 0.5-0.8%.
- 根据权利要求1所述的回收方法，其特征在于，步骤(1)中，所述铵盐和氨水混合得到浸出液，所述浸出液和粗制镍铁合金的液固比为(3-6)：1mL/g。The recovery method according to claim 1, is characterized in that, in step (1), described ammonium salt and ammoniacal liquor are mixed to obtain leachate, and the liquid-solid ratio of described leachate and crude nickel-iron alloy is (3-6): 1mL /g.
- 根据权利要求1所述的回收方法，其特征在于，步骤(1)中，所述氨浸反应的过程中，总氨浓度为4mol/L～9mol/L，当所述铵盐为硫酸铵时，所述铵离子与硫酸根的摩尔比为(2-5)：1。The recovery method according to claim 1, is characterized in that, in step (1), in the process of described ammonia leaching reaction, total ammonia concentration is 4mol/L～9mol/L, when described ammonium salt is ammonium sulfate , the molar ratio of the ammonium ion to the sulfate radical is (2-5):1.
- 根据权利要求1所述的回收方法，其特征在于，步骤(1)中，所述升温的温度为40℃～200℃；加压的压力为0.5Mpa～1.5MPa；反应的时间为2h～10h。The recovery method according to claim 1, wherein, in step (1), the temperature of the temperature rise is 40°C～200°C; the pressure of the pressurization is 0.5Mpa～1.5MPa; the reaction time is 2h～10h .
- 根据权利要求1所述的回收方法，其特征在于，步骤(1)中，所述氨浸反应的过程中，循环通入空气，所述通入空气的流量控制为1.0-3.0L/min。The recovery method according to claim 1, characterized in that, in step (1), in the process of the ammonia immersion reaction, air is circulated, and the flow rate of the introduced air is controlled to be 1.0-3.0 L/min.
- 根据权利要求1所述的回收方法，其特征在于，步骤(2)中，所述还原剂为碳源，所述碳源为碳粉、淀粉、葡萄糖中的至少一种。The recovery method according to claim 1, wherein in step (2), the reducing agent is a carbon source, and the carbon source is at least one of carbon powder, starch, and glucose.
- 根据权利要求1所述的回收方法，其特征在于，步骤(2)中，所述焙烧的温度为200℃-600℃，焙烧的时间为2-8h。The recovery method according to claim 1, wherein in step (2), the roasting temperature is 200°C-600°C, and the roasting time is 2-8h.
- 根据权利要求1所述的回收方法，其特征在于，步骤(3)中，所述碱性缓冲液为氢氧化钠、氢氧化钾或碳酸钠中的至少一种；所述碱性缓冲液的浓度为1～5mol/L，所述 调pH至碱性是将pH调至9～10，所述的反应时间为2～8h。The recovery method according to claim 1, wherein in step (3), the alkaline buffer is at least one of sodium hydroxide, potassium hydroxide or sodium carbonate; The concentration is 1-5 mol/L, the pH adjustment to alkaline is to adjust the pH to 9-10, and the reaction time is 2-8h.
- 权利要求1-9任一项所述的回收方法在回收有色金属中的应用。Application of the recovery method described in any one of claims 1-9 in recovering non-ferrous metals.
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| CN113860397B (en) * | 2021-10-22 | 2022-08-26 | 江西佳纳能源科技有限公司 | Preparation method of nickel sulfate |
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| CN115491497B (en) * | 2022-09-22 | 2024-03-19 | 广东佳纳能源科技有限公司 | Method for recycling valuable metal elements in iron slag and application of method |
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